Detergent compositions consisting essentially of beta-ketoalkyl alkyl sulfoxides and water-soluble alkaline detergency builder salts



United States Patent 3,329,618 DETERGENT COMPOSITIONS CONSISTING ES-SENTIALLY OF fi-KETOALKYL ALKYL SULF- OXIDES AND WATER-SOLUBLE ALKALINEDETERGENCY BUILDER SALTS Warren I. Lyness, Mount Healthy, and David E.OConnor, Cincinnati, Ohio, assignors to The Procter & Gamble Company,Cincinnati, Ohio, a corporation of Ohio No Drawing. Original applicationMar. 30, 1965, Ser. No. 444,068. Divided and this application Sept. 12,1966, Ser. No. 578,467

5 Claims. (Cl. 252138) ABSTRACT OF THE DISCLOSURE Detergent compositionsconsisting essentially of fl-ketoalkyl alkyl sulfoxides and up to 90% ofwater-soluble alkaline detergency builder salts.

This application is a division of copending application Ser. No.444,068, filed Mar. 30, 1965.

This invention relates to sulfoxide derivatives containing keto groupsin the beta position and to methods for synthesizing said derivatives.

Compounds containing both a sulfoxide group and a beta-keto group toseparate the sulfides and sulfones from the desired" sulfoxides.

It can be appreciated, therefore, that an effective method forintroducing a sulfoxide group and a keto group into the same compound atpredetermined sites is desirable. It can be equally appreciated that amethod which permits the formation of compounds containing both keto andsulfoxide groups without the use of high temperatures, corrosiveoxidizing agents and specialized equipment is very desirable.

Accordingly, it is an object of this invention to preparecompoundscontaining both a sulfoxide group and a keto group in the beta position(hereinafter referred to as keto sulfoxides), by methods which avoid theaforesaid defects and in which the advantages hereinbefore indicated areinherent.

It is a more specific object of this invention to provide ketosulfoxides having surface active properties.

It is a yet further object of this invention to provide detergentcompositions containing keto sulfoxide detergents.

The objects of this invention can be accomplished by 3,329,618 PatentedJuly 4, 1967 ice reacting salts of sulfinyl carbanions having theformula 0 R R- '3 M wherein R is a hydrocarbon group containing from 1to about 30 carbon atoms, and wherein R is attached to the sulfur atomof the sulfoxide group by a single covalent bond between carbon andsulfur, wherein R and R are selected from the group consisting ofhydrogen and hydrocarbon groups containing from 1 to about 30 carbonatoms, and wherein R, R and R each contain from 0 to about 10 linkagesselected from the group consisting of ether, thioether and iminolinkages, and from 0 to about 5 amine groups each selected from thegroup consisting of primary, secondary and tertiary amine groups, andare not more reactive with a strong base than a hydrogen atom attachedto a saturated carbon atom adjacent to the sulfoxide group and whereinthe total number of carbon atoms in the sulfoxide compound does notexceed about 32, and not more than two of the hydrocarbon groups in thecompound contain aryl groups, and wherein M is an alkali metal (e.g.,sodium, potassium or lithium) with an acylating agent selected fromthegroup consisting of (1) Carboxylic acid esters having the formula (RO)nR wherein R is a hydrocarbon group containing from 1 to 29 carbonatoms and from O to about 2 ester groups and R represents the alkylportion of the alcohol part of the ester and contains from 1 to about 20carbon atoms and n is an integer from 1 to 3 and corresponds to thenumber of hydroxyl groups originally present on the alcohol,

(2) Acyl chlorides having the formula R )G1).. wherein R has thedefinition hereinbefore given and n is an integer from 1 to 3,

(3) Acid anhydride of monocarboxylic acids having the formula o R Owherein each R has the definition hereinbefore given,

(4) Diesters of carbonic acid wherein R has the definition hereinbeforegiven,

(5) Succinic anhydride, and

(6) Phthalic anhydride.

The symbol used for the sulfoxide group is only a convenientrepresentation-of the structure for purposes of the description of theinvention and is not necessarily indicative of the actual structurewhich is believed to involve a semi-polar bond. This symbol or even moresimply (SO) is used hereinbefore and hereinafter to represent thesulfoxide group.

As used herein, the term hydrocarbon groups refers to both unsubstitutedhydrocarbon groups and substituted hydrocarbon groups containing, forexample, ether linkages. Preferably the substituent hydrocarbon groups(R) in the formulas above and below are alkyl chains, straight orbranched, containing from 1 (to about 22 carbon atoms (e.g., methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl,n-hexyl, n-heptyl, n-octyl, isooctyl, 2- ethylhexyl, diisobutyl,n-nonyl, tripropylene, n-decyl, undecyl, n-dodecyl, tridecyl,n-tetradecyl, pentadecyl, nhexadecyl, n-octadecyl, eicosyl, docosyl,vinyl, propenyl, octenyl, IO-undecenyl, 9-octadecenyl, cyclopentyl,cyclohexyl, cyclohexylmethyl, methylcyclohexyl, 2-cyclohexyldodecyl,12-cyc1ohexyldodecyl, 4-dodecylcyclohexyl and propynyl). Examples ofother groups include aryl groups containing 6 to 12 carbon atoms (e.g.,phenyl, biphenyl and naphthyl); and alkyl aryl groups containing benzeneor naphthalene groups with branched or straight alkyl chains of from 1to about 18 carbon atoms (e.g., benzyl, 2-phenyl-dodecyl,1-methyl-2-phenylethyl, 2-indenyl and naphthylmethyl). R and R are eachselected from the group consisting of hydrogen and hydrocarbon groupswhich are the same as those examples given hereinbefore with respect toR. The presence of certain non-reactive groups in or on the substituentR, R or R groups is permissible. As an example of non-reactive groups,these substituent groups can contain up to about ether and/ or thioetherlinkages. Amino groups can be appended to the chain or imino groups canform a part of the chain with open-chain and/ or cyclic configuration.(R, R and R have the above definitions throughout the specification andclaims.) Thus, R, R or R can represent, for example, such groups as3,6,9,12,1S-pentathiaheptacosanyl;

3,6,9,12,15-pentaoxaheptacosanyl;

3,6,9-trithiaheptacosanyl;

3,6,9-trioxaheptacosanyl;

2-dodecyloxyethyl;

2-octadecyloxyethyl;

2-methoxyethyl;

2-ethoxyethyl;

2-hexyloxyethyl;

2-octyloxyethyl;

2-dodecylthioethyl;

2-octadecylthioethyl;

2-methylthioethyl;

2-ethylthioethyl;

2-hexylthioethyl',

2-octylthioethyl;

1 l-methoxyundecyl;

1 l-methylthioundecyl;

1 l-ethoxyundecyl;

9- or IO-methoxyoctadecyl;

9- or IO-ethoxyoctadecyl;

9- or 10-methylthiooctadecyl;

2-, 3-, or 4-metlroxycyclohexyl;

3- or 4-methylthiocyclohexyl;

3-cyclohexyloxydecyl;

2,5,8,l l,l4-pentamethyl-3,6,9,12,15-

pentaoxaheneicosanyl;

2-tetrahydrofuranyl;

Z-tetrahydrothiophenyl;

tetrahydropyranyl;

2- (tetrahy dropyranyl) -ethyl;

2- Z-tetrahydrofuranyl) -ethyl;

tetrahydrothiofuranyl;

3,6-dioxaheptyl;

3 ,G-dithiaheptyl; 3,6,9-triazaheneieosanyl; JS-aminoethyl;

,B-aminopropyl; ,B-methylaminoethyl; ,B-methylaminopropyl;,B-dimethylaminoethyl; B-dimethylaminopropyl 5-amino-3-azapentyl;S-dimethylamino-3-azapentyl; S-dimethylamino-3-methazapentyl;8-amino-3,6-diazaoctyl; 15-amino-3,6,9, IZ-tetraZapentadecyl;4,6-dimethoxy-2-sym-triazinyl; 4,6-diamino-2-sym-triazinyl; 4-piperidyl;

18- N-piperidyl) -ethyl;

5- (N-piperazinyl) -ethyl;

[3- N-imidazolyl) -ethyl;

[3- (N-morpholino -ethyl;

p- (N-oxazolyl) -ethyl;

B- (N-pyrrolidyl) -ethy1; and 2-thiazo1yl.

Additionally, R can represent, for example, S-N-anilinoethyl;fi-N-anilinopropyl; fi-N-pyridylethyl; 1-methoxy-2- indanyl;fi-N-naphthylaminoethyl; 2-benzoxazolyl and 4,6-dianilino-Z-sym-triazinyl.

It will be understood that more than one sulfoxide group can be presentin the molecule of the sulfoxide starting compound. That is to say therecan be more than one group. Preferably these additional groups are alkylsulfinyl groups and more preferably they are methyl sulfinyl groups.However, the two sulfoxide groups should not be attached to the samecarbon atom since the reactivity of the compound will then be enhancedas explained in US. Patent 3,124,618. Also, if there are not at leastthree aliphatic carbon atoms separating sulfoxide groups, then cleavageof the compound by the base may occur. Sulfoxide groups can be attachedto adjacent carbon atoms on a benzene ring, however. Polymers containingmultiple pendent alkyl sulfinyl groups, e.g., methyl sulfinyl groups,are desirable as sulfoxide starting compounds. The restriction on thenumber of carbon atoms which can be present in the molecule is, ofcourse, different when more sulfoxide groups are present. The number ofcarbon atoms per sulfoxide group should not exceed 32, however.

The preferred sulfoxide starting compound is dimethyl sulfoxide,

because it undergoes the aforementioned reaction with remarkablefacility and is readily available. Other preferred sulfoxide startingcompounds are alkyl methyl sulfoxides, R-SOCH wherein R contains fromabout 2 to about 22 carbon atoms (e.g., dodecyl methyl sulfoxide).

REACTIONS OF ACYL ESTERS The reaction of acyl esters with the salts ofsulfinyl carbanions acylates the sulfoxide and generates concomitantlyan alkoxide ion. It is believed that the reaction proceeds as follows,where sodium methylsulfinylcarbanion is used as an example:

R CCHzSOCHa CHaSOOH2 Na I 6 R -d-oHsooH3Na CHaSOCH:

As hereinbefore mentioned, R in the preceding equations is thehydrocarbon portion of the acyl group. R contains from 1 to about 29carbon atoms and can be an alkyl, aryl, alkyl aryl, or aryl alkyl, e.g.,the acid portion of the ester can be acetic, ste-aric, benzoic,propionic, butyric, isobutyn'c, naphthoic, toluic, para-ethyl-benzoic,phenylacetic, or cinnamic acids. R can contain additional esterifiedcarboxyl groups, e.g., the acid can be a dicar boxylic acid containingfrom 2 to about 12 carbon atoms, such as suocinic or phthalic acids,which is completely esterified. R represents the alkyl portion of thealcohol part of the ester and contains from 1 to about 2-0 carbon atoms,n is an integer from 1 to 3 corresponding to the number of hydroxygroups present on the alcohol. That is to say that the alcohol cancontain up to two additional esterified hydroxyl groups, e.g., the estercan be a triglyceride. Where there are more than one R groups in themolecule they need not all be the same. The total number of carbon atomsin the molecule should not be more than about 60. (R and R have theabove respective definitions throughout the specification and claimsexcept where otherwise specifically defined.)

Instead of adding water in reaction (3) to destroy the keto-sulfinylcarbanion by adding a hydrogen atom to the carbon bearing the negativecharge, a compound with an available hydrogen, such as an alcohol, canbe added which will also add a hydrogen atom to keto-sulfinylcarbanions, or an alkyl halide (R CH X) can be added to alkylate thecarbon between the keto and sulfoxide groups 'by an alkylation reactionwhich forms an alkali metal halide as -a by-product as described in thecopending application of Warren I. Lyness, David E. OConnor and Jim S.Berry, Ser. No. 448,229, now Patent No. 3,288,860.

Examples of acyl ester reactants for use with the sulfinyl carbanionsinclude ethyl benzoate, methyl toluate, dibutyl phthalate, dimethylterephthalate, diethyl isophthalate, ethyl cinnamate, ethyl acetate,methyl acetate, methyl vanillate, methyl anisate, methyl salicylate,methyl anthranilate, methyl nicotinate, methyl veratrate, methylphenylacetate, methyl propionate, methyl butyrate, methyl pivalate,isopropyl myristate, cetyl palmitate, octyl octanoate, methyllignocerate, methyl isovalerate, ethyl laurate, methyl laurate, methylstearate, methyl oleate, methyl linoleate, ethyl palmitate, methylvalerate, ethyl caproate, methyl ca-prate, methyl undecylenate, diethylsuccinate, dimethyl sebacate, dimethyl azelate, diethyl adipate, andmixtures of methyl or ethyl esters prepared from fatty acids derived 5from natural sources such as coconut oil and tallow. Esters of polyolssuch as triglycerides and propylene glycol diester will undergo the samereaction; the triglycerides are preferred reactants from economicconsiderations. Thus, for example, methylsulfinylcarbanion reacts at theester functions of animal or vegetable fats, such as soybean oil orlard, to produce sulfinyl acylation products. Acyl esters, ashereinbefore described, of alcohols containing from one to about threehydroxy groups, when completely esterified with acids containing from 2to 30 carbon atoms and from one to three acid groups (all of which areesterified) and wherein said ester contains a total of from about 3 toabout carbon atoms are useful reactants with the sulfinyl carbanion.

REACTIONS OF ACYL CHLORIDES The acyl chlorides react with the salts ofsulfinyl carbanions as follows, where sodium methylsulfinylcarbanion isused as an example:

o Rfl-iJ-CHzSOCHah-i-DNaCl As hereinbefore stated can represent acidchlorides of both monoand di-carboxylic acids. That is to say It can beeither 1 or 2. Useful acid chlorides include acetyl chloride, butyrylchloride, benzoyl chloride, lauroyl chloride, stearoyl chloride andadipoyl chloride.

REACTIONS OF ACID ANHYDRIDES OF MONOCARBOXYLIC ACIDS Acid anhydrides ofmonocarboxylic acids react with salts of sulfinyl carbanions as follows,wherein R has the definition hereinbefore given and sodiummethylsulfinylcarbanion is used as the example:

(5) f R4C o omsoom na IRA-(Ii) 0 sulfinyl carbanions by undergoing thesame reaction .as the more conventional dicarboxylic acid estershereinbefore discussed. The product of this reaction, however, isdifferent from the product of the reactions of the more conventionaldicarboxylic acid esters. The pro-duct of this reaction will be morefully discussed hereinafter. Examples of carbonate esters which areuseful reactants are dimethyl carbonate, diethyl carbonate and dicetylcarbonate. I

REACTIONS OF SUCCINIC AND PHTHALIC ANHYDRIDES Succinic and phthalicanhydrides differ from the aforementioned anhydrides of monocarboxylicacids in that they contain two potential acid groups on the samemolecule. Therefore, the product of the reaction of these anhydrideswith the alkali salts of the sulfinyl carbanions is unique by virtue ofcontaining a carboxylate group in addition to the groups normally formedby acylation of alkali metal salts of sulfinyl carbanions.

Dimethyl sulfoxide is an excellent solvent for the reactions of thisinvention and in most instances an excess of dimethyl sulfoxide is thepreferred solvent. However, other non-reactive solvents or diluents canbe used, especially other sulfoxide compounds. These solvents should notcontain any reactive constituent either as part of the structure of thesolvent or as part of impurities present in the solvent if maximumyields are desired. The use of solvents which will react with the saltsof the carbanion is generally undesirable. It is recognized, however,that certain reactive compounds can be present as a solvent or as acomponent of a solvent mixture to yield an in situ formation andreaction of the salts of sulfinyl carbanions.

Suitable non-reactive solvents or diluents for the above reactions ofsalts of sulfinyl carbanions and acylating agents and for alkali metalalkanesulfenates and acylating agents as hereinafter more fullydescribed are to be found in such classes of compounds as the aliphaticor aromatic hydrocarbons, aliphatic, aromatic or mixedaliphatic-aromatic ethers, cyclic ethers and amines. Examples ofsuitable non-reactive hydrocarbon solvents include hexane, petroleumether, Stoddard solvent, benzene, toluene and mixed xylenes. Among theether compounds which are suitable as solvents are diethyl ether,dibutyl ether, anisole, diphenyl ether, tetrahydrofuran,1,2-dimethoxyethane and diethylene glycol dimethyl ether. Aminecompounds which can serve as solvents for the reactions of thisinvention and include butylarnine, N-methyl butylamine, anhydrousethylene diamine, pyridine and morpholine. Anhydrous liquid ammonia canalso be used as a solvent. Still another compound which is suitable isN,N- dimethyl formamide. Other similar non-reactive solvents or diluentscan be used with substantially equivalent results.

The rate and course of the above reactions can be affected by the choiceof solvent. The use of mixtures of two or more non-reactive compounds asthe reaction medium is, of course, suitable and in some cases preferableto the use of a single species.

The reactions of this invention are normally carried out at slightlyabove room temperature (25 C.); temperatures of about 50 C. to about 70C. are preferred.

Carbon metal bonds are unstable at elevated temperatures and at 120 C.,for instance, sodium methylsulfinylcarbanion is destroyed. Therefore,elevated temperatures above the decomposition temperature of thecarbanion are undesirable. Lower temperatures than room temperature arenot normally desirable because the speed of the reaction is undesirablydecreased. A temperature range of from about C. to about 100 C. issuitable for carrying out the reactions of this invention.

Z-KETOALKYL ALKYL SULFOXIDES The new and useful compounds produced bythe acylation of the salts of sulfinyl carbanions with the acylationagents hereinbefore described contain at least one sulfoxide group andat least one ketone group. As such, they are useful either as surfaceactive agents, or as intermediates in the preparation of surface activeagents or other useful compounds as hereinafter described.

For example, compounds prepared from the reaction of naturaltriglyceride mixtures such as coconut oil or tallow with sodiummethylsulfinyl carbanion are good surfactants and are useful indetergent formulations.

The compounds of this invention have the formula wherein R is ahydrocarbon group containing fro-m l to about 30 carbon atoms, andwherein R is attached to the sulfur atom of the sulfoxide group by asingle covalent bond between carbon and sulfur, wherein R and R areselected from the group consisting of hydrogen and bydrocarbon groupscontaining from about 1 to about 30 carbon atoms, and wherein R, R and Reach contain from O to about 10 linkages selected from the groupconsisting of ether, thioether and imino linkages, and from 0 to about 5amine groups each selected from the group consisting of primary,secondary and tertiary amine groups, and are not more reactive with astrong base than a hydrogen atom attached to a saturated carbon atomadjacent to the sulfoxide group and wherein the total number of carbonatoms in the sulfoxide compound does not exceed about 32, and not morethan two of the hydrocarbon groups in the compound contain aryl groups,and wherein R contains from 1 to about 29 carbon atoms.

Examples of the compounds which can be formed from this reaction are:

Z-ketotridecyl methyl sulfoxide 2-ketoundecyl methyl sulfoxide2-ketononadecyl methyl sulfoxide 2-keto-10-nonadecenyl methyl sulfoxideZ-ketopentadecyl methyl sulfoxide benzoylmethyl methyl sulfoxideo-aminobenzoylmethyl methyl sulfoxide The first five compounds above aredetergent materials. The last two compounds, which can be formed, forexample, by reacting benzoyl chloride or ethyl benzoate or theamino-substituted products with sodium methylsulfinylcarbanion, areuseful perfume materials.

Those Z-ketoalkyl alkyl sulfoxides which do not have detergentproperties are surface active agents or are useful as intermediates inthe preparation of surface active agents.

The dicarboxylic acid esters and carbonic acid esters can react to formcompounds having two sulfinyl groups and having the formula wherein L isusually 1 but can be 0 for the carbonate esters, and P is either zero(for the carbonate and oxalate esters) or an integer from one to aboutten. Therefore, when both L and P are zero the ester reactants arecarbonate esters; when L is one and P is zero the ester react-ants areoxalate esters, and when L is one and P is an integer, the esterreactants are the esters of dicarboxylic acids such as succinic acid.

For example, the product of a reaction between dimethyl succina-te andtwo moles of sodium methylsulfinylcarbanion is 1,6-bis(methylsulfinyl)hexane-2,5-dione, which is useful either as such or after conversion tothe corresponding diol, as a cross-linking agent for cellulose and wool.When diethyl carbonate is substituted for dimethyl succ-inate, theproduct is bis(methylsulfinyl) ketone which is also a cross-linkingagent for cellulose and wool.

The anhydrides of succinic and phthalic acids react as hereinbeforedescribed to give compounds having the following generic formula whereinR is a hydrocarbon group containing from 1 to about 30 carbon atoms, andwherein R is attached to the sulfur atom of the sulfoxide group by asingle covalent bond between carbon and sulfur, wherein R and R areselected from the group consisting of hydrogen and bydrocarbon groupscontaining from 1 to about 30 carbon 9 atoms, and wherein R, R and Reach contain from to about 10 linkages selected from the groupconsisting of ether, thioether and imino linkages, and from 0 to aboutamine groups each selected from the group consisting of primary,secondary and tertiary amine groups, and are not more reactive with astrong base than a hydrogen atom attached to a saturated carbon atomadjacent to the sulfoxide group and wherein the total number of carbonatoms in the sulfoxide compound does not exceed about 32, and not morethan two of the hydrocarbon groups in the compound contain aryl groups,wherein U is selected from the group consisting of -C H and and whereinT is selected from the group consisting of alkali metals and hydrocarbongroups containing from 1 to about 28 carbon atoms.

S-ALKYLSULFINYL-LEVULINIC ACID DERIVATIVES The reaction of succinicanhydride with the sulfinylcarbanions of this invention producesderivatives of levulinic acid. For example, the reaction of succinicanhydride with sodium methylsulfinylcarbanion would give the sodium saltof S-methylsulfinyl-levulinic acid. Esters of this acid are, forexample, bacteriostatic agents.

ORTHO-CAR BOXYBENZOYLMETHYL ALKYL SULFOXIDES The reaction of phthalicanhydride with the sulfinyl carbanions of this invention gives, as aproduct, an orthocarboxybenzoylmethyl alkyl sulfoxide. For example, theproduct of a reaction of phthalic anhydride with sodiummethylsulfinylcarbanion is the sodium salt of ortho-carboxybenzoylmethylmethyl sulfoxide. The methyl ester, for example, of this material is aperfume material. When the sulfinyl carbanion contains a long chainhydrophobic group, the product is a surface active agent.

SURFACE ACTIVE AGENTS AND DETERGENT COMPOSITIONS The novel 2-ketoalkylalkyl sulfoxides are useful per se as detergent and surface activecompounds or as intermediates in the preparation of detergent andsurface active compounds.

The uses to which surface active compounds can be put are numerous andwell known, e.g., preparing oil-inwater emulsions, textile treatment,dyeing, flotation, preparation of rubber latex, and the like.

Desirably, but not necessarily, the Z-ketoalkyl alkyl sulfoxides areused with alkaline builder materials to form built detergentcompositions, as for example, liquid, bar, flake, granular or tablettedgranular compositions. Such compositions have enhanced detergentcharacteristics due to coaction in aqueous washing compositions betweenthe 2-ketoalkyl alkyl sulfoxides and the alkaline builder material.

Z-ketoal-kyl alkyl sulfoxides which are detergents are those in whichone of the R groups hereinbefore described contains from about 8 toabout 20 carbon atoms and the rest of the R groups are either hydrogenatoms or short alkyl chains containing from 1 to about 3 carbon atoms.Preferred detergents are those which have the formula wherein R is analkyl group containing from about 8 to about 20 carbon atoms. These areincorporated into de- 10 tergent compositions in amounts from about 0.5%to about 50% by weight of the composition.

The detergent compositions of this invention contain from about 0% to90%, preferably from 20% to 90%, of water soluble alkaline detergencybuilder salts, either of the organic or inorganic types, and shouldprovide a washing solution pH of about 9 to about 12. The ratio ofbuilder salts to organic detergent is preferably from about 1:4 to about20:1, preferably from about 0.7:1 to about 9:1. Examples of watersoluble inorganic alkaline detergency builder salts are alkali metalcarbonates, phosphates, polyphosphates, and silicates. Specific examplesof such salts are sodium and potassium tripolyphosphates, carbonates,pyrophosphates, orthophosphates, and hexametaphosphates. Examples oforganic alkaline detergency builder salts'are (1) alkali metal aminopolycarboxylates [e.g., sodium and potassiumethylenediaminetetraacetates, N- (2-hy-droxyethyl)ethylenediaminetriacetates, nitrilo triacetates, andN-(LhydroxyethyD-nitrilo diacetates]; (2) alkali metal salts of phy-ticacid (e.g., sodium and potassium phy-tatessee U.S. Patent 2,739,942);(3) water soluble salts of ethane1-hydroxy-1,1-diphosphonate (e.g., thetrisodium and tripotassium salts see U.S. Patent 3,159,581); (4) watersoluble salts of methylene diphosphonic acid (e.g., trisodium andtripotassium methylene diphosphonate and the other salts described inthe copending application of Francis L. Diehl, Ser. No. 266,025, filedMarch 18, 1963 now Patent No. 3,213,030); (5) water soluble salts ofsubstituted methylene diphosphonic acids (e.g., trisodium andtripotassium ethylidene, isopropylidene, benzylmethylidene, andhalomethylidene diphosphonates and the other substituted methylenediphosphonates disclosed in the copending application of Clarence H.Roy, Ser. No. 266,055, filed March 18, 1963); (6) water soluble salts ofpolycarboxylate polymers and copolymers as described in the copendingapplication of Francis L. Diehl, Ser. No. 269,359, filed April 1, 1963(e.g., polymers of itaconic acid, aconitic acid; maleic acid; mesaconicacid; fum-aric acid; methylene malonic acid; and citraconic acid andcopolymers with themselves and other compatible monomers such asethylene); and- (7) mixtures thereof.

Mixtures of organic and/or inorganic builders can be used and aregenerally desirable. Especially preferred are the mixtures of buildersdisclosed in the copending application of Burton H. Gedge, Ser. No.398,705, filed Sept. 23, 1964, e.g., ternary mixtures of sodiumtripolyphosphate, sodium 'nitrilotriacetate, and trisodium ethane-1-hydroxy-l,l-diphosphonate.

The detergent compositions of this invention can con 7 tain any of theusual adjuv-ants, diluents and additives, for

example, anionic, nonionic, ampholytic, cationic or zwitterionicdetergents, perfumes, anti-tarnishing agents (e.g., sodium and potassiumsilicates and benzotriazole), antiredeposition agents (e.g. alkali metaland ammonium salts of carboxymethyl cellulose), bacetrio-static agents,dyes or pigments (including optical brighteners), suds builders, sudsdepressors, and the like, without detracting from the advantageousproperties of the composition. Examples of anionic detergents aresodium-coconut soap; sodium dodecylbenzene sulfonate and potassiumt-allow alkyl sulfate. Examples of nonionic detergents aredodecyldimethylamine oxide and the condensation product of coconut fattyalcohol with 5.5 moles of ethylene oxide. An example of a zwitterionicdetergent is 3-(N,N-dimethyl-N- hexadecylammonio)2-hydroxypropane-1-sulfonate. An example of an ampholytic detergent issodium-3-dodecylamino-propionate. An example of a cationic detergent iscetyltrimethylammonium bromide.

Normally the organic detergent components, the builders and the minoringredients are incorporated into the composition prior to conversioninto fiinal product form, e.g., detergent granules, flakes, etc., butthey can also be added individually in the form of particles or asliquids.

The following examples are illustrative but not limiting to the practiceof this invention.

Example I 22 g. (0.10 'mole) of ethyl laurate in 50 ml. of dimethylsulfoxide was added to 0.12 mole of methylsulfinylcarbanion (sodiumsalt) in 75 ml. of dimethyl sulfoxide and the mixture was stirred fortwo hours at 2530 C., at which time the reaction was essentiallycomplete. The reaction mixture was allowed to stand overnight at roomtemperature and then ten ml. of water was added to the flask and thenthe entire mixture was poured into 200' ml. of ice water. Theprecipitate wasfiltered off and was taken up in acetone. The acetone wasfiltered and then evaporated to give a residue. The water-dimethylsulfoxide solution was extracted three times with ethyl acetate whichwas then evaporated to a residue. The residues were combined andrecrystallized twice from hexane to yield 6.7 g. of Z-ketotridecylmethyl sulfoxide (melting point: 81- 82 C.).

When glyceryl trilaurate was substituted for ethyl lau- -rate in theabove reaction a 51% yield of 2-ketot-ridecyl methyl sulfoxide wasobtained. This 2-ketotridecyl methyl sulfoxide is useful as a detergentsurfactant.

In a similar reaction ethyl acetate was reacted withmethylsulfinylcarbanion to give 2-ketopropy1 methyl sulfoxide, which isuseful as an intermediate in the preparation of detergent surfactantsand other surface active agents.

When either acetic anhydride or acetyl chloride are substituted for theethyl acetate in this example, substantially equivalent results areobtained in that the 2- ketopropyl methyl sulfoxide is produced.Substitution of lauric anhydride and lauroyl chloride for the ethyllaurate in this example gives substantially equivalent results in theformation of the 2-ketotridecyl methyl sulfoxide occurs.

When diesters such as diethyl carbonate and dimethyl succinate arereacted with the sodium salt of the methylsulfinylcarbanion, thereaction occurs at both ester groups and the products are1,6-bis(methylsulfinyl) hexane-2,5 dione and (bis(methylsulfinyl) ketonerespectively which are useful as cross-linking agents for cellulose andwool.

When either suocinic anhy-dride or phthalic anhydride is reacted withthe sodium salt of the methylsulfinylcarbanion the products are,respectively, the sodium salt of S-rnethylsulfinyllevulinic acid (theesters of this acid are bacteriostatic agents) and the sodium salt ofortho carboxybenzoylmethyl methyl sulfoxide (the methyl ester of thiscompound is a perfume material).

When in the above example the following groups are substituted for themethyl in the sodium salt of methylsulfinylcarbanion, and/ or when thefollowing groups are substituted either Wholly or in part "for oneand/or two hydrogen atoms on the canbanion so that the total number ofcarbon atoms in the resulting alkali metal sulfinyl carbanion compoundis less than 32, and so that there are no more than two aromatic groupspresent in the molecule, substantially the same results are achieved inthat the corresponding alkali metal sulfinyl carbanions react with theacylating agents to produce the corresponding keto sulfoxide compounds:

methyl; ethyl; -p py isopropyl;

isobutyl; n-pentyl; isopentyl; n-hexyl; n-heptyl; n-octyl;

isooctyl; Z-ethylhexyl; diisobutyl; n-nonyl; tripropylene; n-decyl;undecyl; n-dodecyl; tridecyl; n-tetradecyl; pentadecyl; n-hexadecyl;n-octadecyl; eicosyl; docosyl; vinyl; propenyl; octenyl; lO-undecenyl;9-octadecenyl; cyclopentyl; cyclohexyl; cyclohexylmethyl;methylcyclohexyl; 2-cyclohexyldodecyl; l2-cyclohexyldodecyl;4-dodecylcyclohexyl; p py y phenyl; biphenyl; naphthyl; benzyl;2-phenyl-dodecyl; l-methyl-Z-phenylethyl; Z-indenyl; naphthylmethyl;3,6,9,l2,15-pentathiaheptacosanyl; 3,6,9,l2,1S-pentaoxaheptacosanyl;3,6,9-trithiaheptacosanyl; 3,6,9-trioxaheptacosanyl; 2-dodecyloxyethyl;Z-octadecyloxyethyl; Z-methoxyethyl; 2-ethoxyethyl; Z-hexyloxyethyl;2-octyloxyethyl; Z-dodecylthioethyl; 2-octadecylthioethyl;Z-methylthioethyl; 2-ethylthioethyl'; 2-hexylthioethyl;2-octylthioethyl; 1 l-methoxyundecyl; 1 l-methylthioundecyl; 1l-ethoxyundecyl; 9- or IO-methoxyoctadecyl; 9- or IO-ethoxyoctadecyl; 9-or lO-methylthiooctadecyl; 2-, 3-, or 4-methoxycyclohexyl; 3- or4-methylthiocyclohexyl; 3-cyclohexyloxydecyl; 2,5 ,8, 1 1,14-pentamethyl-3,6,9, 12, l 5 -pentaoxaheneicosanyl;Z-tetrahydrofuranyl; Z-tetrahydrothiophenyl; tetrahydropyranyl;2-(tetrahydropyranyl)-ethyl; 2- Z-tetrahydrofuranyl -ethyl;tetrahydrothiofuranyl; 3,6-dioxaheptyl; 3,6-dithiaheptyl;3,6,9-triazaheneicosanyl; li-aminoethyl;

13 B-aminopropyl; S-methylaminoet-hyl; fi-methylaminopropyl;fl-dimethylaminoethyl; fl-dimethylaminopropyl; -amino-3-azapentyl;5-dimethylamino-3-azapentyl; 5 -dimethylamino-3 -methazapentyl;8-amino3,6-diazaoctyl; 15-amino-3,6,9,12-tetrazapentadecyl;4,6-dimethoxy-2-sym-triazinyl; 4,6-diamino-2-sym-triazinyl; 4-piperidyl;

' B- N-piperidyl) -ethyl;

3- N-piperazinyl -ethyl; ,G-(N-imidazolyD-ethyl;

;3-( N-pyrrolidyl) -ethyl;

2-thiazolyl;

fi-N-anilinoethyl;

B-N-anilinopropyl;

l-methoxy-Z-indanyl; fl-N-naphthylaminoethyl; 2-benzoxazolyl;4,6-dianilino-2-sym-triazinyl; and mixtures thereof.

When in the above example the corresponding potassium and lithium saltsof the carbanions .are substituted either Wholly or in part for thesodium salts, substantially the same results are achieved in that thereaction less than that amount removed by the organic solvent from clothcleaned in the sodium tallow alkyl sulfate. Therefore, negative numbersare better than the reference surfactant and positive numbers are worsethan the reference surfactant. Sodium tetrapropylene benzene-sul-fonate, a standard commercial detergent surfactant,

with the acylating agents followsessentially the same Example II Thedetergency effectiveness of the detergents of this invention wasdetermined by washing naturally soiled swatches of desized print clothfor ten minutes in an aqueous solution'of the detergent to be evaluatedunder the following conditions: I

(1) Water temperaturel30 F.

(2) Water hardness-'--7 gr.

(3) Detergent concentration0.02% by weight.

(4) Sodium tripolyphosphate builder concentration- 0.05% by weight.

(5) Water pHl0.

A miniature machine (the Tergotometer) having normal reciprocatingagitation was used. (Tergotometer testing is described in DetergencyEvaluation and Testing, by J. C. Harris, Interscience Publisher, Inc.1954, p. 60.)

After washing, rinsing and drying, the amount of lipid soil remaining onthe swatch was determined by extraction with organic solvent. Bycomparison with similar determinations of the amount of lipid soil insimilarly soiled swatches washed under the same conditions with sodiumtallow alkyl sulfate the relative effectiveness of the detergentsurfactant can be determined. The results given are in percent by weightof lipid soil removed from the cloth by the organic solvent, either moreor is included to show the effectiveness of the compounds of theinvention relative to commercial products.

The results of the tests are summarized below:

EX. Detergent surfactant Test result II Z-ketotridecyl methyl sulfoxide+18 Sodium tetrapropylene benzene sulfonate (reference) +30 Thedetergent in Example II is a good detergent v material.

When in the above example carbonates; pyrophosphates; ethylenediaminetetraacetates; N-(Z-hydroxyethyl)-ethylenediamine triacetates;nitrilo triacetates; N- (Z-hydroxyethyl)-nitrilodiacetates; phytates;ethane-l-hydroxy-l-diphosphonates; methylenediphosphonates; ethyl idenediphosphonates; isopropylidene diphosphonates; benzylmethylidenediphosphonates; chloromethylidene diphosphonates; salts of polymers ofitaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid,methylene maleic acid and citraconic acid; salts of copolymers of theabove acids with themselves; salts of copolymers of the above acids withethylene; salts of copolymers of the above acids with themselves andethylene (the foregoing named polymers and copolymers have molecularweights of at least 350 and equivalent weights of from to 80 based onthe acid forms); and mixtures thereof in the form of their sodium,potassium, triethanolammonium, diethanolammonium, andmonoethanolammonium salts and mixtures thereof are substituted, eitherwholly or in part, e.g., a 50% substitution, for the sodiumtripolyphosphate builder substantially equivalent results are obtainedin that for each builder substitution the detergent agents used in theprocess of this invention are effective cleaning agents.

Examples III-XVI g. of sodium hydride (0.40 mole, 56% dispersion inmineral oil), was suspended in 500 ml. of dimethyl sulfoxide (dried bydistillation at reduced pressure from calcium hydride and storageover'5A Molecular Sieve) and heated With stirring at 60-65 C. for 2 /2hours under a slow nitrogen sweep until hydrogen evolution ceased. Thesolution of the resulting sodium methylsulfinylcarbanion was cooled tol820 and maintained at that temperature by ice-water cooling while 0.20mole of the indicated ester was dripped in over a period of 20 minutes.The solution was allowed to Warm to room temperature, then poured ontocrushed ice containing 26 g. (0.5 mole) of ammonium chloride. Theaqueous solution was extracted with two 300 ml. portions of chloroform.The chloroform layer was dried with anhydrous magnesium sulfate andevaporated at reduced pressure, with a vacuum pump being required toremove the residual dimethyl sulfoxide. The product was recrystallizedfrom 600 ml. of acetone giving the indicated yields of the indicatedproducts having the indicated melting points.

Yields r Percent Esters Sultoxides Melting by Weight Point, C. ofRecrystallized Material Il-C 7H 5COOCH n-CnHaaCOCHzSOCHa 97-98 6743000113 o1n-ooomsoom 83-84 37 cum-Q-oooom CHaO-COCII2SOCH3 102-103 52oF3--oooo1 a on-Qooomsoom 111-112 36 (CHahCHCHzCOOCHa(CHa)zCHCH2COCH2SQCH3 .a 84 I1-C9H1gCOOCH3 Il-CgHmCQCHzSOCHG 75. 5-76. 574 n-CmHmCOOCzHs Il-CmHmCOCHzSOCH: 88-89 1 56 CsH 7CH=CHC7H COCzH5CBHI'ICHZCHC'IHHCOCHZSOCH3 53-54 47 F@COOCH3 F-GCOCHzSOCHa 92. 6-93. 2 349 CH2=CHC H COOCH CH=CHCgHwCOCHzSOCHa 73-74 66 C 7Ha5COOCHCnHssCOCHzSOCHa 97-98 2 70 COOCzHs -COCHzSOCHa 153. 2-153. 6 2 24 CH9COOCH3 C H9COCHzSOCHs 37-37. 3 34 @oooom COCH2SOCH:4 so-s7 45 1 Theyield is that of twice recrystallized material.

2 The yield is that of thrice recrystallized material.

3 The procedure differs in that enough dried tetrahydrofuran or1,2-din1ethoxyethane was added to depress the freezing point to 0-5 0.,at which temperature the ester was added.

What is claimed is: 3-. The detergent composition of claim 1 whereinthere 1. A detergent composition consisting essentially of is at leastabout water soluble alkaline detergency from about 0.5% to about 50% ofa material having builder salts. the formula 4. The detergentcomposition of claim 1 wherein the R1 0 ratio of builder salts toorganic detergent is from about 1 g 0.7:1 to about 9: l.

5. The detergent composition of claim 1 wherein the detergency buildersalts are selected from the group conwherein one f the R groups, R, 1 24 is an alkyl sisting of sodium tripolyphosphate, sodium nitrilotrigroupcontaining from about 8 to about 20 carbon atoms acetate, andethane-l-hydroxy-l,l'diphosphollateand the rest of the R groups areeither hydrogen atoms or short alkyl chains containing from about 1 toabout References Clted 3 carbon atoms, and from about 0% to about 90% ofUNITED STATES PATENTS water soluble alkaline detergency builder salts,the ratio 2 327 966 8/1943 Morey 260 593 of builder salts to organicdetergent being from about 2802033 8/1957 g y-a; 26O 592 1:4to about20:1.

2. The detergent composition of claim 1 wherein R ON ROSDOL, PrimaryExamimm and R in the formula are hydrogen atoms, R 1n the Y formula is amethyl group and R is an alkyl group con- DARDEN Asslstmt Exammer'taining from about 8 to about 20 carbon atoms,

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF FROM ABOUT 0.5% TOABOUT 50% OF A MATERIAL HAVING THE FORMULA